1, 2-diamino-1-alkene compounds



Vhew

2,941,005 1,2-DIAM1NO-1-ALKENE COD/[POUNDS John E. Mahan, Bartlesville,kla., assignor to Phillips Petroleum Company, a corporation of DelawareFiled July 29, 1955, Ser. No. 525,347

4 Claims. (Cl. 260-583) No Drawing.

other aspect this invention relates to a method for propelling rockets.In another aspect this invention relates to 1,2-diamino-l-alkenes as newcompounds. In still another aspect this invention relates to new fuelcompositions comprising a liquid hydrocarbon and at least one of said1,2-diaminol-alkenes.

This application is a continuation-in-part of my c0- pending applicationSerial No. 366,381, filed July 6, 1953 which in turn is acontinuation-in-part of my copending application Serial No. 257,973,filed November 23, 1951, now abandoned.

- My invention is concerned with new and novel rocket propellants andtheir utilization. A rocket or jet pro pulsion device, such as isdiscussed herein is defined as a rigid container for matter and energy,so arranged that a portion of the matter can absorb the energy inkinetic, form and subsequently eject it in a specified direction.Thetype rocket to which my'invention is particularly applied is thattype rocket propulsion device designated as a pure rocket, i.e., athrust producer which does not make use of its surrounding atmosphere. Arocket of the type with which my invention is concerned is propelled inresponse to the steps of introducing a propellant mais thus necessarythat the combustion chamber, although being strong enough to stand highpressure and tempera-. ture, need be only large enough toinsurecombustion. The flow of liquid propellants into the combustion chambercan be regulated at will so that the thrust resulting from continuous orintermittent bursts of power can be sustained. Intermittent burning ofthe fuel contributes to a longer life of the combustion chamber and ofthe thrust nozzle.

-Various methods and liquid combinations'have been found to be useful asrocket propellants. 'Some propellants consist of a single material, andare termed monoprop'ellan Those propellants involving two materials aretermed bipropellants and normally consist of an 2,941,05 Patented June14, 1960- with aniline or furfural alcohol as the hypergolic fuelcomponent.

When employing 90-100 percent nitric acid, i.e., white fuming nitricacid as theoxidizer in a rocket bipropellant fuel, it is oftennecessary, dependent upon the specific fuel component, to obtain moreeffective ignition than would normally be obtained, by dissolving from 6to 23 percent by weight of nitrogen dioxide in white fuming nitric acid,thereby forming"red fuming nitric acid. A fuel component of thebipropellant type described herein is spontaneously ignited uponcontacting the oxidizer. For this reason such a bipropellant material isreferred to herein as being hypergolic. A ratio of oxidizer tohypergolic fuel, based upon stoichiometric amounts, can be utilizedwithin the limits of 0.5 :l to 1.5:1 if desired. The efliciency ofcombustion is less at a ratio below 1:1 and the use of the oxidizer isless economical at ratios above 121. However, practical considerationmay neces: sitate the use of higher ratios, 'even as high as 6:1.

Each of the following objects of the invention will be obtained by thevarious aspects of this invention.

I thrust to a rocket-type device. Another object is to provide as newcompounds the 1,2-diamino-l-alkenes characterized by the structural,formula given and defined below. Another object is to provide animproved fastburning fuel. Other and further objects will be apparent tothose skilled in the art upon study of the accompanying disclosure.

In accordance with the broad aspects of this invention, I have foundthat organic polyamines, either in the presence or absence of normallyliquid hydrocarbons form a fuel component which is highly"hypergolic andsuitable for use in the propulsion of rockets, guided missiles, and thelike, in conjunction with an oxidizer. I have further found that theseorganic polyamines together with selected mercaptans, both more fullysetforth hereinbelow, either in the presence or absence of normally liquidhydrocarbons, form a fuel component which is also highly hypergolic andsuitable for the uses set forth above. The fuels of the presentinvention are composed of (1) at least one organic polyamine or mixturethereof, or (2) at least one organic polyamine or mixture thereof withat least one selected mercaptan, either of the latter components beingsuitable in a major. or minor amount. When a selected mercaptan is usedas one of .the fuel constituents, it is preferred that the mixturescontain at least 10 percent of the organic poly-.-

plication Serial No. 257,973, filed November 23, 51,

there are disclosed and now being claimed those organic polyaminesselected from the group consisting of 1,3 butanediarnine,1,2-propanediamine, triethylenetetramine, and tetraethylenepentamine.

In accordance with the invention in my copending application Serial No.366,381, filed July 6, 1953 there are disclosed and now being claimed.those organic polyamlnes which contain at least two groups attached toone or more carbon atoms, wherein Ris selected from the groupconsisting, of a hydrogen at'o'rii' and hydrocarbon radicals selectedfrom the group consistin'g of alli yl, a'lken'yl, cycloalkyl,cycloalkenyl, aryl, alk'aryl', and a'ralkyl radicals and the hydrocarbonof said polyainine is selected from the same group, the total numberof'c'arb'o'n atoms in said polyamine being not greater than 30 and atleast one R of at least two groups-being a hydrocarbon radical.

In both of the said cope'n'ding applications the carbon atom to' whichthe substituent group is attached may be a cyclic (.carbocyclic) carbonatom, a carbon atom of a side chain group attached to a yclic-(car'bocyclic) carbon atom or'a carbon atom of an acyclic molecule.

The following organic polyarnines are useful in the practice oftheinvention of my copending application Serial 'No; 366,381: thealiphatic polyamines which include the various alkane polyamines such asN,N'-diethy1-l,4 hexanediamine; N,N,N,N'-tetraallylmethylenediamine;N,N,N',N' -tetramethylmethylenediamine;N,N,N',N-tetramethylethane-1,2-diarnine;N,N,N',N-tetramethylbutane-1,4-diamine; VN,N,N',N'-tetrarnethy1propane-1,3-diamine; andN,N,N',N-tetramethylpropane-1,Z-diamine.

Various alkenylene polyamines are also very efficient hypergolicmaterials and include V N,N,N',N' tetramethylpropene 1,3-diamine; N,N,N',N'atetraallylpropene-1,3-diarnine; N,N,N,N'-tetraethylpropene-1,3-diamine; N,N,N,NT :tetrn Z-methylallyl)prop ene- 1 ,3 -dia.mine; N,N ,N',N'-tetracrotylpropene-1,3-diamine;N,N-diallyl-N',N'-di(3-bu1tenyl)propene-1,3-diamine;N,N,N',N'-tetraallyl-Zmethylpropene-1,3-diamine; N,N'-diallyl-N,N-dimethylprop erie-l ,3 -di amine;N,N'-dicrotyl-N,N'-dipropylpropene-1 ,3 -diamine;E,N,N,N'-tetramethyl-2-methylpropene-l,3-diamine; and

e like.v

In addition to the above recited specific compounds, the total reactionmixture or fractions thereof from the preparation of N,N,N',Ntetraallyl-, tetramethylallyl-, or tetracrotylpropene-l,3-diamine, isuseful as constituent of hypergolic fuel compositions according to thesaid- Serial No. 366,381. These compounds are kno-wnin the art and canbe prepared by the manner described in US. Patent 2,565,529 by C. W.Smith, wherein a suitable alpha, beta -unsaturated aldehyde is reactedwith one or more'secondary monoamines having attached to the nitro genatom at least one alkenyl group with an olefinic b ondinthe 2,3-positionrelative to the hydrogen atom or by other similar methods. I

As indicated hereinbefore, and in accordance with my .4- groupscontaining only carbon, hydrogen and nitrogen atoms.

Further according to the invention there are now provided as newcompounds the 1,2-diamino-l-alkenes characterized by the structuralformula R I R \N-C=CN/ R/ 7 IR) '\R wherein: R is a member selected fromthe group consisting of a hydrogen atom, alkyl, cycloalkyl, alkenyl, and

cycloalkenyl hydrocarbon radicals; each R is a memher selected from thegroup consisting of alkyl, cycloalkyl, alkenyl and cycloalkenylhydrocarbon radicals, and the .Rs can be alike and unlike; the totalnumber of carbon atoms in the molecule does not exceed 24; and the totalnumber of carbon atoms? in Ry. does not exceed 8., It is to beunderstood that herein and in the claims the above named hydrocarbonradicals includes the various combinations of said radicals suclr asalkylcycloalkyl, cyclo= .alkenylalkyl, cycloalkylalkenyl,alkylcycloalkenyl, alkenyl-N,N,N',N'-tetramethyl-1,2-diarnino8,7-dimethyl-1,7-octadiene, N',N,N',-Ntetrabutyl' 2 ethylcyclohexyl-l,Z-diarninoethylene, and

N,N- dimethyl N,N-"-did-hexyll-cyclopentenyl-1,2-diamino-l-butene, N,N-'dimethyl N,N'-di(Z-butenyl)-5-cyclopentyl-l',2'diw aminol,4-pentadiene,N,N' dimethyl N,N'-di(2-cyclopentylethyl) -l,2-diamino-4-methyL1-pentene, I N,N' diethyl. N,N'-di(3 ethyl2-cyclopentenyl)1,2-di

aminefl-propene,

- N,N' di'm'ethyl N-N' -di(5-allyl-2-cycloheireny1) 1,231-

. 'ary' amine as disclosed and claimed in the copending.

aminoethylene.v V I have further found that the new compounds of myinvention are especially useful as hypergolic fuels. Indeed, s'aidnewcornp'ounds are superior to any previously known hypergols shownbythe data 'given below in Example XIV and Table II. Examples I to XII,given below, areincluded' for comparison purposes to show thesuperiority of my new compounds as hypergolic fuels 7 vas compared withother organic polyar'nin'es.

' The new compounds of my invention can be prepared 7 by reacting undersuitable conditions, an alpha-halo-alde hyd'e, having at l'e'astonehydrogen atom attached to the carbon atom alphat'o the aldehyde group,with a secondapplication of R. C; Doss and H. W. Best, Serial No.

525,346, filed rui za, 1955, now Patent No. 2,881,217, issued April 7,19591 Said method oflpr'epafrin'g my new compounds is illustrated below?in Example XIII and 7 Table I invention, the'amin'o groups of theabove=desoribed poly Representative ha'lo-aldehydewhich can be used inpreparing my new compounds include, among'othei's, the following:chloroacetaldehyde, 2-brom0-p1'0pionaldehyde,

eit'maeimaea ae d Representative secondary amineswhich caii be used inpreparaing my new compounds include, among others, the following:dimethylamine, diethylamine, methylethylamine, dibutylamine,dipropylamine, diisopropylamine, dial-lylamine, andN-methylcyclohexylamine.

The fuel constituents of the-present invention are hypergolic in anundiluted state and are alsohypergolic when admixed with non-hypergolicmaterials, particularly hy drocarbons, in a state of dilution as 'highas70 percent by Suitable non-hypergolic materials which golic fuels inaddition to white or red fuming nitric acid and can be used in thebipropellant fuel compositions of our invention. Suitable oxidantsinclude materials such as hydrogen peroxide, ozone, nitrogen tetroxide,liquid oxygen and mixed acids, especially anhydrous mixtures of-nitricand sulfuric acids such as 80 to 90 percent by volume of white or redfuming nitric acid and to percent by volume anhydrous or fuming sulfuricacid. It is within the scope of this invention to employ, preferablydissolved in the oxidizer, ignition catalysts or oxidation catalysts.These oxidation catalysts include certain metal salts, such as thechlorides and naphthenates of iron, zinc, cobalt and similar heavymaterials.

As an added feature of this invention my new compounds are also usefulfor providing fast burning fuels for use in rocket engines and the likewherein a hypergolic' fuel is not necessarily required. For example, thefuel components of this invention are dispersed in a hydrocarbon, suchas the hydrocarbon diluents described above. Even if the resultingsolution is not hypergolic with an oxidant such as fuming nitric acid,it can be used together with an oxidant and a suitable igniter as arocket propellant. These fast burning fuels are particularly useful if,for various reasons, a hypergolic fuel is not desired or required. Theorganic polyamines of this invention may be added to a hydrocarbon fuelin a minor amount, usual- .1y from 1 to 20 percent by volume of thetotal mixture to produce fast-burning fuels which are non-hypergolic.Suitable fast-burning fuels comprise from 1 to 20 percent by volume ofan organic polyamine described above with 90 to 99 percent by volume ofa petroleum fraction gasoline boiling range. Specifically, such a fuelcan comprise between 1 and 20 percent by volume of a 1,2-diamino-l-'alkene and 80 to 99 percent by volume normal heptane.

As pointed out above, selected mercaptans can be used to form a portionof the hypergolic fuel constituents of this invention in admixture withthe above described organic polyamines. Likewise selected mercaptans canbe used with my new 1,2-diamino-l-alkenes. The mercaptans which aresuitable for use as such a hypergolic fuel constituent include compoundsof the general formula RSH, wherein K is-selected from the groupconsisting of alkyl and alkenyl groups containing from 3 to 10 carbonatoms. Illustrative of the mercaptans used in this invention aretert-butyl mercaptan, isopropyl mercaptan, allyl mercaptan, n-butylmercaptan, n-hexyl mercaptan, terthexyl mercaptan, tert-octyl mercaptan,nonyl mercaptan, tert-decyl mercaptan, 2-butene l-thiol,3-butene-l-thiol, isobutyl mercaptan, and the like.

A fuel of the present invention, i.e., mixtures consisting of, at leastone 1,2-diam ino-l-alkene and at least one mercaptan are hypergolic inan undiluted state and are amines 5 also hypergolic when admixed withnon-hypergolic ma: terials, particularly those normally liquidhydrocarbons set forth above, when using such hydrocarbons in amounts ashigh as 50 percent by volume of hydrocarbon when white fuming nitricacid is used as the oxidant. v The invention is further illustrated inthe following ex amples. The reactants and their proportions and thespecific ingredients-are presented as being typical and not to beconstrued as unduly limiting the invention.

' EXAMPLE I p Maximum Dilution, Percent volume n-heptane or benzenePolyamine Oxldant rab imnednmma.

o 4. triethylenetetramlne tetraethylenepentamine...

-' 1 n-Heptane diluent. i Benzene diluent.

EXAMPLE II A reaction flask fitted with thermometer, dropping funnel,reflux condenser and stirring unit was charged with a mixture of 50grams of finely powdered anhydrous potassium carbonate, grams of diethylether and 194 grams of diallylamine. As the mixture was stirredvigorously, 56 grams of acrolein were slowly added with cooling tomaintain the reaction mixture between 10 and 15 C. (50 to 59 F.). Afterall the acrolein had been added, the reaction mixture was kept at 5 to10 C. (41 to 50 F.) and stirred for 17 hours. The contents of thereactor were then filtered to remove the solid desiccant; a dark-redfiltrate was recovered. The ether and low boiling components, includingunreacted acrolein and diallylamine, were removed by fractionaldistillation. The higher boiling material was then transferred to avacuum distillation apparatus and distilled under reduced pressure. Asummary of the distillation results is presented in the following table:a I a N,N,N',N-tetraallylpropene-1,3-diamine and the other materialsrecovered from the fractionation of Example I were tested forspontaneous ignition employing fuming nitric acid as the oxidant. Thetemperature of the fuel and oxidant was maintained at room temperature(21 C.). In each test 0.13 ml. of the fuel or a diluted solution thereofwas dropped into a 1" x 8" test tube con pro edure otExamplelv.Results.aresetgforthbelowz ('n-heptane) was employed to determine theamount of V axln l m e dilution which each fuel would tolerate andretain its hy- 7 Fuel oxidant I g g; 722E116; pergolic properties. Theresultsrare set forth in. the foll. V Retgggfin t Iowmg I THypergohclty" p d ffifiii atgo li Plastic resi ue.

- fifif Fuel l ii gng ggrlastlclresldue dlssolvedinn-heptane.---. i: 28;

ofHyper-'1 J. I

golicity l 7 Fraction No-1 .Q 4-,. E I Z3 -Ajrlml for the preparation-ofN,NgN,N' -tetra llylpm- Fraction No. 2 (N,N,N,Netetraallylpro- 3g pene1.,3.-diamine was conducted 1n the manner described f m R I: 7 inExamplel except that the reaction mixture. was stlrred Fmmn i {WFNAmfor16. hours. After filtering off thepotassium carbonate, a Y the reactionmixture was stripped of ether. Then half of In addition to the roomtemperature tests previously the de-etheri-fied. materiabwas refractionated to remove rib ,N',N',- r allyl-1,3-diaminopropene and everything upto diallylamineunder reduced pressure other materials recovered from thefractionationproce- (h d temperature 35 ,C., corn); The. remaining halfdure of Example I were also tested for spontaneous igniofthis materialvwas refractionated to'remo ve everything tion at 40 C. Prior to testing,the temperature of the up to and including diallylamine under reducedpressure fuel and oxidant was lowered to 4() C. Testswere con- (headtemperature, 117 C., corn). These two materials Y ducted employing 0.13ml. of fuel or a diluted solution were tested for self-ignitionproperties at 21 C. and at thereof and 0.3 ml. of fuming nitric'acid.Results are 25 -4.0 C. in the manner set forth in previous examples.recorded below. Results are recorded below:- r r Maximum Per- MaximumDtcent Dilution 7 Test lution with I Q withn-heptane Fuel 'TernpebOxldant n-heptane Fuel Oxidant with "ature, wlthRetenv Retention of C.tlon of V Hypergolicity Hypergoliclty at 40 C. V k

. I RFNA 70 Grude roduct (ether removed)- 21 V Fraction No. 2(N,N,N,N-tetraallylpr0- $fi"-- p A pene-lfidiamine). RFNA"" 40 Do 10Fraction No. 3 10 70 f Crude product (ether and 60 r diaglylamineremoved). V 40 'In addition to the above tests, the crude reaction mix-0 N ture obtained from the, procedure of Example I was also 7 V testedfor self-ignition properties. Prior to testing, ether & .EXAMPLE VI 7 fip f mammals were f??? by geatmg A drop test apparatus comprising aninjection nozzle f E mix i Warm i 61 u inserted to within 1 of. thebottom of a 1"): 8" test uce 'f g g e a Wa er asplra esu S tube wasemployed to determine the ignition delay in are 6 5 milliseconds rN,N,N,N'-tetraallylpropeneeI,3-diamine.

I A small quantity of fuel (0.2 ml.) was placed in the botl tom of thetest tube and 0.3 ml. of'whit'e fuming nitric cent Dllutiorr, FuelOxidant with n-lleptane acld was in ected mm the fuel. A constantpressure nitrog gfi gen surge chamber provided a source of approximatelyHypergolicity 40 p.s.i.g; pressure to inject the oxidizer into the fuel.vA solenoid coil actuated the injector to provide an accurately CrudeReaction Mixture from the Run FNA Not diluted metered/amount of oxidant.The ignition delay interval a fig f' (that and low WFNAI, Do. wasdetermined as the time between contact of the oxigznaterals removed). VD0 RFNA... 60. dlzerw th the fuel and the presence of flame as sensed'by a photocell. 7

r V N, N ,N",N'-tetraallylpropene-1,3-diarnine was tested em- EXAMPLE Vploying' the apparatus described and was found to have A, run; for thepreparation of N',N,N',N'-tetraallylproan 1 lgmtlondelayof6-3jm11hsewndS- pene-1,3-dia-mine was conducted in-the manner describedI extremely short delay compared to k inExarnplel except that thereaction mixture was stirred" lhypergollc fuels, for x P ffurfurylalcohol, a 19 9* for 12.5 hours. The reaction mixture was very darkrhypergohc fuel; had an lgmtlon delay of 2731111155? in color andviscous. This material was. distilled to re- Fi as deltermmed. the mapparatus and test P move unreacted diallylamine and other volatilematerials cedureleaving a black, plastic residue in'thekettle. Thismaterial 7 EXAMPLE VII fi f9? silmliallwus lgmtlon emP1Qy1ngf umingN,MN,N'-Tetramethylpropene-1,3-diarnine was premmc afld ll Willie.conducted W111i the pared from dimethylarnine and acrolein bysubstantially fuel and Q ldant maintained at room. temperature (21 the,same procedure. as previously employed. for C.). In the first test, asmall particle of the solid, plastic N,N,N,N'-tetraallylpropene-l,3-cliamine; The crude ma.- residue was dropped into 0.3 ml. of. fumingnitric acid'in terial,. in, 73.8 percentv yield, was distilled in an18inch a 1" x 8" test tube. in addition thisresiduewas dissolved column.A 30. percent: theoretical yield of distilled in ptane and themaximumdilution that the material product was obtained, along with 22percent solid'kettle would tolerateand. maintain its self-ignitionproperties residue. A was. determined. 0.13, mlrof fuel solution, wasemployed These materials wereexamined for dilution data'and with. 0.3.ml. of fuming nitric acid as describedinthetest 1T ignition delay-'withfithe drop tester usingstandard tecl'vv niqu'est Toluene DilutionB.P., Ignition Delay,

Material 0. a Room temp. 40 0. milliseconds RFNA WFNA RFNA WFNAN,1N3,N,N-Tetramethylpropene- 1 48 1. 4589 70 7O 10 15.5 24 C.

Crude N ,N ,N,N'-Tetramethyl- 1. 4668 70 70 20 10.5 24 C.

propene-1,3-diamine. Plastic kettle product Hypergolic 1 At 103 mm. Hg.

EXAMPLE VIII manner described hereinbefore. Tests were conducted Each ofthe fuel mixtures described hereinbelow was 15 with fuel and oxidant atroom temperature (21 C.)

tested for spontaneous ignition employing fuming nitric Results arerecorded below.

Maximum Percent Dilution Fuel Composition Oxldant with n- Heptane withRetention of Hypergolicity Red Fuming Nitric Acid No ignition. f jfi i zT x {White Fuming Nitric Acid Do.

9 6 Red Filming Nitric Acid described above dissolved in tertbutylmercaptan. }White Fuming Nitric Acid 50.

acid as the oxidant. -The temperature of the fuel and 30 EXAMPLE Xoxidant was maintained at 21 C. In each test, 0.13 ml. i of the fuel ora diluted solution thereof was dropped into A run for the preparation ofN,N,N,N' tetraallyl a 1 inch by 8 inch test tube containing 0.3 ml. offuming propene-1,3-diamine was conducted in the manner def nitric acid.The inert diluent was employed to determine scribed in Example IIIexcept that the reaction mixture the amount of dilution which each fuelwould tolerate wasstirred for 16 hours. After filtering oif thepotassium and retain its hypergolic properties. The results are setcarbonate the reaction mixture was stripped of ether. A forth below.portion of this material was 'refractionated to remove Maximum Per-'cent Dilution Fuel Composition Oxidant with n- Heptane with Retention ofHypergolicity Red Fuming Nitric Acid No ignition. gert'butyl 'ifg WhiteFilming Nitric Acid Do. 7 v Ween i i e Red Fumin Nitric Acid 20a1ly1propene-13-diamine in tertb Y butyl memapfim White Fuming NitricAcid- 10. v

1 Prepared by the run described in Example III.

EXAMPLE IX everything up to and including diallylamine under reducedpressure (head temperature 117 C., corr.). This material was admixedwith tert-butyl mercaptan in varying proportions and the fuelcompositions so formed were tested for self-ignition properties by theprocess described in previous examples. Results are set forth below. I v

A run for the preparation of N,N,N,N-tetraallylpropene-1,3-diamine wasconducted in the manner described in Example III except that thereaction mixture was stirred for 12.5 hours. The reaction mixture wasMaximum Percent Dilution Fuel Composition Oxidant with'n- Heptane withRetention of Hypergolicity 100 percent tert-butyl mercaptan g g% fi gg2g No gg 10 percent crude N,N,N',N'-tetraal.lyldF m Nit A 201,3-diaminopropene(etheranddialiyl m 3 01 amine removed). White FummgNitric Acid 20.

very dark in color and viscous. This material was dis- EXAMPLE XI.stilled to remove unreacted diallylammeand pther volatile Sever-a1 ofthe alkane polyamines and alkenylene poly: .materials. leaving a black,plastic residue in the kettle. iamines were tested f ignition delays 'ap tester .A small amount of this residue was dissolved in fertinjectingwhile fuming nitric acid into a small quantitj 'of butyl mercaptan(readily soluble) and the composition fuel and determining the ignitiondelay interval between so formed was tested for self-ignition propertiesin the the contact of the acid and'fuel and the presence of flame -11 assensed by a photocell. The materials and ignition delays are set forthbelow.

Material Fuming Nitric Acid, MillisecondsN,N,N;N-tetramethylmethylenediamine- N ,N ,N,N-Tetramethylpropanc-1,3-diamine- N,N,N,N-Tetramethylpropane-1,2-diamineEXAMPLE Xll intervalbetween the contact of the acid' and fuel and thepresence of flame, as sensed by a photocell. The materials and ignitiondelays are set forth below.

Ignition Delay with White sewn.

- N i- H enema-momma 12 VT able [Pressuremm. mercury.]

Overhead Distillate Distillate, Refrac- Out No Temp Collected, tiveIndex 7 0. gms.

9. 1 l. 4643 9. 8 1. 4655 g. 1. 4658 Product 413 11 4648 Mainlymethylcyclopentanecollected in a trap maintained in a Dry Ice-acetonebath to prevent vapors from entering vacuum pump.

milliseconds V ylene and N,N,N',N-tetramethy1-1,2-propanediamine.

Ignition Delay, Milliseeonds, at 75 F.

Material Red White Fumlng Fuming Nitric Nitric Acid AcidN,N,N,N-tetramethylethane-1,Z-dialnine 9. 3N,N,N,N-Tctramethylbutane-1,2-diamine.- I 14N,N,NQNGTetramethyl-Lbutene-3;4-diamine. -4. 1.N,N,N,N-2-Pentamethylpropane-l,B-diamine 22 N=,N,N ,N-Tetrarneth3dbutane-l,4-(1iamine. 7. 4 7N,N,Nf,N-Tetramethyl-2-butenc-1,4-diamine. 4.3 4'N,N,N,N-Tetramethy1hexane-l,G-diamine 8. 8 5

EXAMPLE XIII 7 To a one liter glass reaction vessel there was added 200milliliters of methylcyclopentane and 220 milliliters of dimethylamine.The reaction vessel was placed in an acetone-Dry Ice bath and, aftercooling to' 8 C., 186 grams of a percent aqueous solution ofchloroacetaldehyde was added dropwise with stirring. The temperature ofthe reaction mixture was maintained between 10 and 0 C. for theapproximately 30 minutes required to add the chloroacetaldehyde. Thetemperature of the black colored mixture was permitted to rise to roomtem-- I perature (about 25 C.) and stirred 2 hours at this tem-'perature;

The aqueous layer of the reaction mixture was sepa- A sodium fusion wasmade on Cut Number 5 and a qualitative test for halogen indicated nonewas present. Solutions of potassium permanganate and bromine wereabsorbed by the product, indicating the presence of a double bond. Atitration of a portion of the product,

made with hydrochloric acid, caused decomposition yielding the freeamine. v 7 g V Cuts 4 and 7 were hydrogenated in the presence of nickelin a Parr hydrogenation bomb at 40 p.s.i-g. and room temperature. Therefractive index of the hydrogenated sample was 1.4180 at 25 C. ascompared with 1.4170 at 25 C'. for a sample ofN,N,N',N'-tetramethyl'ethanediamine. These testsserved to characterizethe product as N,N,N',N'-tetramethyl-1,2 diaminoethylene.

The product yield was 38 percent of theoretical based on thechloroacetaldehyde charged.

EXAMPLE XIV A drop test apparatus comprising an injection nozzleinserted to within. 1" of the bottom of a l" x 8" test tube was employedto determine the ignition delay in ofN,N,N',N'-tetramethyl-1,2-diaminoeth- A small quantity of fuel (0.2 ml.)was placed in. the bottom of the test tube and 0.3 :ml. of white fumingnitric acid was injected into the fuel. A constant pressure nitrogensurge chamber. provided a source of approximately 40 p.s.i.g. pressureto inject the oxidizer into the fuel. A solenoid coil actuated theinjector to provide an accurately metered amount of oxidant. Theignition delay interval was determined as the time between contact ofthe oxidizer with the fuel and the presence of flame as sensed by a"photocell. Table II' gives the data obtained on the ignition delaysobtained by this method.

This value was obtained using a different acid and at a dificrent timefrom the value given in Example XI. V

As can be seen from the data given in the above Table II, the compoundN,N,N',N-tetramethyl-1,2-diaminoethylene, which is representative of thenew compounds of my invention, exhibits an ignition delay which issuperior to that of N,N,N,N'-tetramethyl-1,2 propanediamine, or any ofthe other. hypergols tested in the other examples. These data show thatmy new hypergols are superior to any other hypergols previous- 7 1yknown prior to my invention.

The superiority of my new compounds is further shown by a comparisonwith ethylene diamine, a known hypergolic fuel. Ethylene diamine has anignition delay of 929 milliseconds at 75 F. as determined by the sameapparatus and test procedure employed in Example 7 XIV.

As will be evident to those skilled in the art, various modifications,substitutions and changes may be made or followed in the light oftheforegoing disclosure without departing from the spirit or scope ofthis invention;

I claim:

-1. A 1,2-diamino-1-a1kene selected from the group consisting ofN,N,NN-tetramethy1 1,2 diaminoethylene; N,N,N',NtetIaethy1-1,2-diaminoethylene; and N,N'-dimethy1-N,N'-diethy1-1,2-diamiuoethy1ene.

2. N,N,N',N'-tetramethy1-1,2-diaminoethylene.

3. N,N,N,N'-tetraethy1-LZ-diaminoethylene.

4. N,N' dimethyl N,N' diethy1 1,2 diaminoethylene.

References Cited in the file of this patent UNITED STATES PATENTSCarmody July 10, 1956

1. A 1,2-DIAMINO-1-ALKENE SELECTED FROM THE GROUP CONSISTING OFN,N,N''N''-TETRAMETHYL - 1,2 - DIAMINOETHYLENE,N,N,N'',N''-TETRAETHYL-1,2-DIAMINOETHYLENE, ANDN,N''DIMETHYL-N,N''-DIETHYL-1,2-DIAMINOETHYLENE.